Mercaptosilanes
View Patent ↗Mercaptosilanes are disclosed of the formula I wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 . They are prepared by a procedure in which a silane of the formula II is subjected to a catalyzed reaction with an alkyl polyether R 1 —H, R 7 —OH being split off, the molar ratio of the alkyl polyethers R 1 —H to the silane of the formula II is at least 0.5 and R 7 —OH is separated off from the reaction mixture continuously or discontinuously. They can be used in shaped articles.
1. A composition comprising a mixture of mercaptosilanes of the formula I,
wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 , where R 5 is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average 3 to 10, and R 6 comprises at least 11 C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,
wherein one R 2 is an ethoxy group and the other R 2 is an R 1 , C1-C12 alkyl, or R 7 O group,
where R 7 is H, methyl, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group,
where R 8 is a C1-C30 branched or unbranched, alkyl or alkenyl group,
R 3 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, and
R 4 is H, CN or (C═O)—R 9 , where R 9 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.
2. The composition according to claim 1 , wherein R 1 has a molecular weight distribution.
3. The composition according to claim 1 , wherein R 6 is C 13 H 27 .
4. The composition according to claim 1 , and further comprising
and/or hydrolysis and/or condensation products thereof.
5. The composition according to claim 1 , wherein R 2 is a C1-C12 alkyl or R 7 O group, where R 7 is H, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group.
6. The composition according to claim 1 , wherein R 2 is an R 1 , C1-C12-alkyl or R 7 O group and R 1 is a member selected from the group consisting of:
—O—(C 2 H 4 —O) 5 —C 11 H 23 , —O—(C 2 H 4 —O) 5 —C 12 H 25 , —O—(C 2 H 4 —O) 5 —C 13 H 27 , —O—(C 2 H 4 —O) 5 —C 14 H 29 , —O—(C 2 H 4 —O) 5 —C 15 H 31 , —O—(C 2 H 4 —O) 3 —C 13 H 27 , —O—(C 2 H 4 —O) 4 —C 13 H 27 , —O—(C 2 H 4 —O) 6 —C 13 H 27 , —O—(C 2 H 4 —O) 7 —C 13 H 27 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 10 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 11 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 13 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 14 CH 3 , —O—(CH 2 CH 2 —O) 3 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 4 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 6 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 7 —(CH 2 ) 12 CH 3 ,
7. The composition according to claim 1 , wherein R 2 is R 1 - and R 1 is a member selected form the group consisting of
—O—(C 2 H 4 —O) 5 —C 11 H 23 , —O—(C 2 H 4 —O) 5 —C 12 H 25 , —O—(C 2 H 4 —O) 5 —C 13 H 27 , —O—(C 2 H 4 —O) 5 —C 14 H 29 , —O—(C 2 H 4 —O) 5 —C 15 H 31 , —O—(C 2 H 4 —O) 3 —C 13 H 27 , —O—(C 2 H 4 —O) 4 —C 13 H 27 , —O—(C 2 H 4 —O) 6 —C 13 H 27 , —O—(C 2 H 4 —O) 7 —C 13 H 27 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 10 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 11 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 13 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 14 CH 3 , —O—(CH 2 CH 2 —O) 3 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 4 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 6 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 7 —(CH 2 ) 12 CH 3 ,
8. An inert organic or inorganic support having absorbed therein a composition according to claim 1 .
9. An organic or inorganic support having been pre-reacted with a composition according to claim 1 .
10. A process for the preparation of a composition according to claim 1 , wherein at least one silane of the formula II
wherein R 10 is an R 7 O group and R 7 has the abovementioned meaning,
R 11 is identical or different and is an R 10 or C1-C12-alkyl group,
R 3 and R 4 have the abovementioned meaning, is catalytically reacted with an alkoxylated alcohol R 1 —H, wherein R 1 has the abovementioned meaning, splitting R 7 —OH off, and separating R 7 —OH off from the reaction mixture continuously or discontinuously.
11. The process according to claim 10 , wherein the alkoxylated alcohol R 1 —H is an ethoxylated alcohol.
12. The process according to claim 10 , wherein the alkoxylated alcohol R 1 —H is a propoxylated alcohol.
13. A rubber composition comprising:
(A) a rubber or a mixture of rubbers,
(B) a filler, and
(C) a composition according to claim 1 .
14. The rubber composition according to claim 13 , further comprising:
(D) a thiuram sulfide and/or carbamate accelerator and/or the corresponding zinc salts,
(E) a nitrogen-containing co-activator,
(F) optionally further rubber auxiliaries, and
(G) optionally further accelerators,
and the weight ratio of accelerator (D) to nitrogen-containing co-activator (E) is equal to or greater than 1.
15. A process for the preparation of the rubber composition, which comprises mixing rubber or a mixture of rubbers, a filler, optionally further rubber auxiliaries and a composition according to claim 1 in a mixing unit.
16. The process according to claim 15 , and further comprising adding a thiuram sulfide and/or carbamate accelerator and/or the corresponding zinc salts, a nitrogen-containing co-activator, optionally adding a rubber auxiliary, and optionally adding an accelerator,
wherein the weight ratio of the accelerator to the nitrogen-containing co-activator is equal to or greater than 1.
17. A shaped article containing a composition according to claim 1 .
18. The shaped article according to claim 17 which is a pneumatic tires, tire tread, cable sheathing, hose, drive belt, conveyor belt, roller covering, tire, shoe sole, sealing ring or damping element.
19. A mercaptosilane of the formula I,
wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 , where R 5 is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average 3 to 10, and R 6 comprises at least 11 C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,
R 2 is identical or different and is an R 1 , C1-C12 alkyl or R 7 O group, where R 7 is H, methyl, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group, where R 8 is a C1-C30 branched or unbranched, alkyl or alkenyl group,
R 3 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, and
R 4 is H, CN or (C═O)—R 9 , where R 9 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.
20. A composition comprising a mixture of mercaptosilanes of the formula I according to claim 19 wherein R 1 has a molecular weight distribution.
21. The mercaptosilane according to claim 19 , wherein m is on average 5.